A compound having an N,N-bis(2-hydroxy-3-chloropropyl)amino group is useful as an intermediate for polyfunctional glycidylamine based epoxy compounds. Polyfunctional glycidylamine based epoxy compounds derived from a compound having an N,N-bis(2-hydroxy-3-chloropropyl)amino group are compounds widely used in the organic chemistry and polymer chemistry fields and compounds useful in diverse fields for industrial uses as fine chemicals, raw materials of pharmaceuticals and agricultural chemicals, and raw materials of resins as well as electronic information materials, optical materials and the like.
Furthermore, polyfunctional glycidylamine type epoxy compounds, when hardened by various hardening agents, generally make hardened materials excellent in mechanical properties, water resistance, chemical resistance, heat resistance, and electrical characteristics, and are utilized in a wide variety of fields such as adhesives, paints, laminates, and composite materials.
A manufacturing method for a common polyfunctional glycidylamine type epoxy compound is carried out by producing a compound having an N,N-bis(2-hydroxy-3-chloropropyl)amino group through an addition reaction between an amine compound and epichlorohydrin in a batch type reaction scheme and causing a cyclization reaction of the production through dehydrochlorination with an alkali.
However, if the addition reaction between an amine compound and epichlorohydrin is carried out by a batch type reaction scheme, rapid heat generation is often involved and, if a reaction accelerating agent such as a catalyst is added to increase the reaction rate, rapid heat generation occurs, leading to a risk of a runaway of the reaction.
Therefore, Japanese Examined Patent Publication (Kokoku) No. SHO 53-124226 proposes a method using a batch type reaction apparatus equipped with a cooling hose within a reaction vessel and in which after epichlorohydrin and water are charged thereinto, an amine compound is gradually dropped while heat is removed to maintain an appropriate reaction temperature.
International Publication WO 2013/089006 proposes a method in which a reaction accelerating agent such as an organic acid is slowly dropped into a system in which an amine compound has been dissolved in epichlorohydrin.
Meanwhile, Japanese Unexamined Patent Publication (Kokai) No. 2009-203425 discloses a method in manufacture of glycidyl ethers which, using a solid acid catalyst, manufactures chlorohydrin ether, an intermediate for a glycidyl ether, in a fixed-bed flow scheme.
However, in the manufacturing method for a polyfunctional glycidylamine type epoxy compound described in JP '226, since the amine compound is dropped while the reaction is controlled, the dripping time is long and, furthermore, to remove reaction heat, a special reaction apparatus equipped with a cooling hose within the reaction vessel is necessary. Furthermore, in the method described in WO '006 in which a reaction accelerating agent is slowly dropped into a system in which an amine compound has been dissolved in epichlorohydrin, if the dripping speed of the reaction accelerating agent is great, the reaction immediately progresses, leading to a risk of a runaway of the reaction so that there is a need to sufficiently control the dripping speed of the reaction accelerating agent. Thus, the method has a problem as a safe industrial manufacturing method.
Meanwhile, if the addition reaction between an amine compound and epichlorohydrin is carried out in a fixed-bed flow by using the solid acid catalyst as described in JP '425, the reaction progresses in an early period of the reaction but gradually decreases in the reaction rate. The decreases occur because amine, which is a reaction substrate, comes to remain adsorbed to acid points on the solid acid catalyst which are reaction activity points so that the acid points are poisoned. Hence, if the solid acid catalyst is used in the fixed-bed flow reaction, the reaction does not stabilize and, furthermore, the catalyst loses activity in a short time so that the catalyst is frequently replaced, posing a problem for stable industrial production.
That is, in manufacture of a compound having an N,N-bis(2-hydroxy-3-chloropropyl)amino group, an industrial manufacturing method that is high in production efficiency and high in safety has not been established yet.
Therefore, a manufacturing method that efficiently and safely produces on an industrial scale a compound having an N,N-bis(2-hydroxy-3-chloropropyl)amino group has been demanded.
It could therefore be helpful to provide a method of manufacturing a compound having an N,N-bis(2-hydroxy-3-chloropropyl)amino group highly efficiently and safely on an industrial scale.